Bis(2,2-dinitro­prop­yl)formal

Liu, F.; Dai, H.; Huang, Z.; Liu, Y.; Kou, X.

doi:10.1107/S1600536809010642

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o903

doi:10.1107/S1600536809010642

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Bis(2,2-dinitropropyl)formal

Fei Liu,^a Huajun Dai,^a Zhong Huang,^b Yonggang Liu ^b and Xingming Kou ^a ^*

^aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, and ^bChina Academy of Engineering Physics, Mianyang 621900, People's Republic of China
^*Correspondence e-mail: kouxm@scu.edu.cn

(Received 11 March 2009; accepted 23 March 2009; online 28 March 2009)

The complete molecule of the title compound [systematic name: bis(2,2-dinitropropoxy)methane], C₇H₁₂N₄O₁₀, which was synthesized by the condensation reaction between 2,2-dinitropropanol and paraformaldehyde in methylene chloride, is generated by crystallographic twofold symmetry with one C atom lying on the rotation axis. In the crystal structure, molecules are linked into chains running parallel to the b axis by intermolecular C—H⋯O hydrogen-bond interactions, generating rings of graph-set motif R₂²(14).

Related literature

For the applications and chemistry of the title compound, see: Garver et al. (1985 ); Hamilton & Wardle (1995 ); Adolph (1991 ); Hamilton & Wardle (1997 ). For graph-set motifs, see: Bernstein (1995 ).

Experimental

Crystal data

C₇H₁₂N₄O₁₀
M_r = 312.21
Monoclinic, C 2/c
a = 23.330 (3) Å
b = 6.207 (3) Å
c = 10.009 (6) Å
β = 109.60 (3)°
V = 1365.6 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 291 K
0.48 × 0.44 × 0.28 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
1404 measured reflections
1255 independent reflections
863 reflections with I > 2σ(I)
R_int = 0.008
3 standard reflections every 100 reflections intensity decay: 1.5%

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.138
S = 1.09
1255 reflections
98 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4ⁱ	0.97	2.59	3.509 (3)	158
C1—H1B⋯O4ⁱⁱ	0.97	2.59	3.509 (3)	158
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z.

Data collection: DIFRAC (Gabe & White, 1993 ); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010642/rz2302sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010642/rz2302Isup2.hkl

checkCIF report

Comment top

The title compound is an important energetic material used in propellant and explosive formulations (Garver et al. 1985; Hamilton & Wardle, 1995). It was also combined with liquid bis(2,2-dinitropropyl)acetal (BDNPA) to prepare the BDNPF/A energetic plasticizer (Adolph, 1991; Hamilton & Wardle, 1997). Here we report the crystal structure of the title compound.

The molecule of the title compound (Fig. 1), has crystallographically imposed two-fold symmetry. The average of N—O bond length is 1.204 (3) Å. The dihedral angle formed by the planes through the nitro group is 74.3 (2)°. The O(1)—C(2)—C(3)—N(1), O(5)—N(2)—C(3)—C(4) and O(4)—N(2)—C(3)—C(4) torsion angles are 172.59 (17), -176.2 (2) and 5.6 (3) ° respectively. In the crystal structure, the molecules are linked into chains running parallel to the b axis by intermolecular C—H···O hydrogen interactions (Table 1) generating rings of graph set motif R²₂(14).

Related literature top

For the applications and chemistry of the title compound, see: Garver et al. (1985); Hamilton & Wardle (1995); Adolph (1991); Hamilton & Wardle (1997). For graph-set motifs, see: Bernstein (1995).

Experimental top

The title compound was synthesized by reacting 2,2-dinitropropanol (6.0 g) with paraformaldehyde (0.6 g) in the presence of concentrated sulfuric acid as catalyst in methylene chloride below 5°C. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a diethyl ether/mineral ether (1:6 v/v) solution.

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Atoms labelled with the suffix 2 are generated by the symmetry operator (1-x, y, 1/2-z).

Bis(2,2-dinitropropoxy)methane top

Crystal data top

C₇H₁₂N₄O₁₀	F(000) = 648
M_r = 312.21	D_x = 1.519 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 23 reflections
a = 23.330 (3) Å	θ = 5.2–8.7°
b = 6.207 (3) Å	µ = 0.14 mm⁻¹
c = 10.009 (6) Å	T = 291 K
β = 109.60 (3)°	Block, colourless
V = 1365.6 (11) Å³	0.48 × 0.44 × 0.28 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 1.9°
Graphite monochromator	h = −28→20
ω/2θ scans	k = 0→7
1404 measured reflections	l = −12→12
1255 independent reflections	3 standard reflections every 100 reflections
863 reflections with I > 2σ(I)	intensity decay: 1.5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.138	w = 1/[σ²(F_o²) + (0.0654P)² + 0.7176P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1255 reflections	Δρ_max = 0.18 e Å⁻³
98 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (3)

Crystal data top

C₇H₁₂N₄O₁₀	V = 1365.6 (11) Å³
M_r = 312.21	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 23.330 (3) Å	µ = 0.14 mm⁻¹
b = 6.207 (3) Å	T = 291 K
c = 10.009 (6) Å	0.48 × 0.44 × 0.28 mm
β = 109.60 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
1404 measured reflections	3 standard reflections every 100 reflections
1255 independent reflections	intensity decay: 1.5%
863 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.09	Δρ_max = 0.18 e Å⁻³
1255 reflections	Δρ_min = −0.17 e Å⁻³
98 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.54239 (7)	0.5416 (3)	0.21472 (18)	0.0661 (6)
O2	0.68680 (8)	0.8202 (3)	0.51558 (17)	0.0706 (6)
O3	0.70016 (9)	1.0217 (3)	0.3547 (2)	0.0854 (7)
O4	0.60961 (13)	0.8225 (4)	0.0432 (2)	0.1153 (10)
O5	0.57606 (12)	1.0244 (4)	0.1735 (3)	0.1154 (9)
N1	0.67637 (8)	0.8730 (3)	0.3932 (2)	0.0538 (5)
N2	0.60412 (11)	0.8729 (4)	0.1542 (2)	0.0702 (7)
C1	0.5000	0.4161 (6)	0.2500	0.0721 (11)
H1A	0.5211	0.3241	0.3297	0.087*	0.50
H1B	0.4789	0.3241	0.1703	0.087*	0.50
C2	0.58346 (10)	0.6513 (4)	0.3320 (2)	0.0619 (7)
H2A	0.5991	0.5550	0.4124	0.074*
H2B	0.5636	0.7721	0.3596	0.074*
C3	0.63384 (9)	0.7279 (3)	0.2821 (2)	0.0470 (6)
C4	0.67114 (13)	0.5524 (5)	0.2509 (4)	0.0887 (10)
H4A	0.7000	0.6135	0.2122	0.133*
H4B	0.6450	0.4542	0.1835	0.133*
H4C	0.6924	0.4765	0.3368	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0497 (9)	0.0705 (11)	0.0702 (11)	−0.0102 (8)	0.0098 (8)	−0.0145 (8)
O2	0.0670 (11)	0.0859 (12)	0.0506 (10)	−0.0086 (9)	0.0086 (7)	−0.0062 (9)
O3	0.0912 (13)	0.0750 (13)	0.0901 (14)	−0.0353 (11)	0.0306 (11)	−0.0070 (10)
O4	0.179 (3)	0.1115 (18)	0.0553 (12)	−0.0540 (17)	0.0396 (14)	−0.0049 (12)
O5	0.1221 (19)	0.0748 (14)	0.127 (2)	0.0347 (14)	0.0122 (15)	0.0233 (13)
N1	0.0481 (10)	0.0533 (11)	0.0610 (12)	−0.0045 (9)	0.0193 (9)	−0.0076 (9)
N2	0.0834 (15)	0.0650 (14)	0.0552 (13)	−0.0133 (12)	0.0137 (11)	0.0046 (11)
C1	0.0401 (16)	0.0499 (18)	0.114 (3)	0.000	0.0094 (17)	0.000
C2	0.0580 (13)	0.0718 (15)	0.0523 (13)	−0.0174 (12)	0.0138 (10)	−0.0065 (11)
C3	0.0464 (11)	0.0457 (11)	0.0454 (11)	0.0006 (9)	0.0107 (9)	−0.0038 (9)
C4	0.0676 (16)	0.0807 (19)	0.108 (2)	0.0146 (14)	0.0159 (15)	−0.0383 (18)

Geometric parameters (Å, º) top

O1—C1	1.394 (3)	C1—H1A	0.9700
O1—C2	1.416 (3)	C1—H1B	0.9700
O2—N1	1.211 (2)	C2—C3	1.500 (3)
O3—N1	1.205 (2)	C2—H2A	0.9700
O4—N2	1.202 (3)	C2—H2B	0.9700
O5—N2	1.198 (3)	C3—C4	1.491 (3)
N1—C3	1.514 (3)	C4—H4A	0.9600
N2—C3	1.528 (3)	C4—H4B	0.9600
C1—O1ⁱ	1.394 (3)	C4—H4C	0.9600

C1—O1—C2	113.52 (16)	O1—C2—H2B	110.7
O3—N1—O2	124.98 (19)	C3—C2—H2B	110.7
O3—N1—C3	118.63 (19)	H2A—C2—H2B	108.8
O2—N1—C3	116.20 (18)	C4—C3—C2	114.6 (2)
O5—N2—O4	126.0 (3)	C4—C3—N1	107.70 (18)
O5—N2—C3	116.5 (2)	C2—C3—N1	109.75 (17)
O4—N2—C3	117.5 (2)	C4—C3—N2	112.8 (2)
O1—C1—O1ⁱ	112.1 (3)	C2—C3—N2	106.23 (18)
O1—C1—H1A	109.2	N1—C3—N2	105.44 (18)
O1ⁱ—C1—H1A	109.2	C3—C4—H4A	109.5
O1—C1—H1B	109.2	C3—C4—H4B	109.5
O1ⁱ—C1—H1B	109.2	H4A—C4—H4B	109.5
H1A—C1—H1B	107.9	C3—C4—H4C	109.5
O1—C2—C3	105.36 (18)	H4A—C4—H4C	109.5
O1—C2—H2A	110.7	H4B—C4—H4C	109.5
C3—C2—H2A	110.7

C2—O1—C1—O1ⁱ	70.17 (16)	O3—N1—C3—N2	−31.8 (3)
C1—O1—C2—C3	165.8 (2)	O2—N1—C3—N2	152.91 (19)
O1—C2—C3—C4	−66.1 (3)	O5—N2—C3—C4	−176.2 (2)
O1—C2—C3—N1	172.59 (17)	O4—N2—C3—C4	5.6 (3)
O1—C2—C3—N2	59.1 (2)	O5—N2—C3—C2	57.6 (3)
O3—N1—C3—C4	88.8 (3)	O4—N2—C3—C2	−120.7 (2)
O2—N1—C3—C4	−86.4 (3)	O5—N2—C3—N1	−58.9 (3)
O3—N1—C3—C2	−145.9 (2)	O4—N2—C3—N1	122.9 (2)
O2—N1—C3—C2	38.9 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱⁱ	0.97	2.59	3.509 (3)	158
C1—H1B···O4ⁱⁱⁱ	0.97	2.59	3.509 (3)	158

Symmetry codes: (ii) x, −y+1, z+1/2; (iii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₇H₁₂N₄O₁₀
M_r	312.21
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	23.330 (3), 6.207 (3), 10.009 (6)
β (°)	109.60 (3)
V (Å³)	1365.6 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.48 × 0.44 × 0.28

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1404, 1255, 863
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.138, 1.09
No. of reflections	1255
No. of parameters	98
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱ	0.97	2.59	3.509 (3)	158
C1—H1B···O4ⁱⁱ	0.97	2.59	3.509 (3)	158

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1, −y+1, −z.

Acknowledgements

The authors thank Mr Zhi-Hua Mao of Sichuan University for the X-ray data collection.

References

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